CN104271641A - Compositions of resin-linear organosiloxane block copolymers - Google Patents
Compositions of resin-linear organosiloxane block copolymers Download PDFInfo
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- CN104271641A CN104271641A CN201380020774.4A CN201380020774A CN104271641A CN 104271641 A CN104271641 A CN 104271641A CN 201380020774 A CN201380020774 A CN 201380020774A CN 104271641 A CN104271641 A CN 104271641A
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- linear
- block copolymer
- organosiloxane
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Links
- 125000005375 organosiloxane group Chemical group 0.000 title claims abstract description 246
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 140
- 239000000203 mixture Substances 0.000 title claims description 86
- 238000000034 method Methods 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims description 101
- 239000011347 resin Substances 0.000 claims description 101
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 90
- 239000007787 solid Substances 0.000 claims description 79
- 239000002585 base Substances 0.000 claims description 61
- 229920001577 copolymer Polymers 0.000 claims description 60
- TUPZKTSKLSDAFI-UHFFFAOYSA-N [O].C[SiH](C)C Chemical compound [O].C[SiH](C)C TUPZKTSKLSDAFI-UHFFFAOYSA-N 0.000 claims description 55
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- -1 trialkylsiloxy compound Chemical class 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000002834 transmittance Methods 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910020175 SiOH Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004032 superbase Substances 0.000 claims description 6
- 150000007525 superbases Chemical class 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 150000002923 oximes Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 239000008247 solid mixture Substances 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- 125000003118 aryl group Chemical group 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 239000000523 sample Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 230000008859 change Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 150000001282 organosilanes Chemical class 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 9
- 238000007711 solidification Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008719 thickening Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- AACDMFYQIDJLBH-UHFFFAOYSA-N [O].CN(C)[SiH3] Chemical compound [O].CN(C)[SiH3] AACDMFYQIDJLBH-UHFFFAOYSA-N 0.000 description 4
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 3
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- BTHCBXJLLCHNMS-UHFFFAOYSA-N acetyloxysilicon Chemical compound CC(=O)O[Si] BTHCBXJLLCHNMS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000002518 distortionless enhancement with polarization transfer Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000009685 knife-over-roll coating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 238000001998 small-angle neutron scattering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
A process is disclosed for preparing a resin-linear organosiloxane block copolymer. The resin-linear organosiloxanes block copolymers prepared by the disclosed process may provide optically solid compositions which may be considered as 'reprocessable'.
Description
The cross reference of related application
The U.S. Provisional Patent Application No.61/613 that patent application claims on March 21st, 2012 submits to, the rights and interests of 532, whole disclosures of this temporary patent application are incorporated to way of reference, as herein complete illustrate.
Background technology
Photodiode (LED) and solar panel use encapsulation coating to protect electronic package from the impact of environmental factors.This protective coating must be optically transparent with the maximum efficiency guaranteeing these devices.In addition, these protective coatings must be tough and tensile, durable, lasting, and be easy to apply.But many coatings available at present lack toughness, are not durable, do not apply lastingly and/or not easily.Therefore, need to differentiate protectiveness and/or functional coat in many emerging technology areas always.
Summary of the invention
Embodiment 1 relates to a kind of method for the preparation of organopolysiloxane segmented copolymer, and the method comprises:
I) make
A) there is the linear organosiloxane of following formula:
R
1 q(E)
(3-q)SiO(R
1 2SiO
2/2)
nSi(E)
(3-q)R
1 q，
Wherein each R
1be C independently when occurring at every turn
1to C
30alkyl or the hydrolysable group containing at least one carbon atom,
N is 10 to 400,
Q is 0,1 or 2,
E is the hydrolysable group containing at least one carbon atom, and
B) in its formula, comprise [the R of at least 60 % by mole
2siO
3/2] organosiloxane resins of siloxy units, wherein each R
2be C independently when occurring at every turn
1to C
20alkyl,
React in c) organic solvent
To form resin-linear Organosiloxane block copolymer;
Wherein select step I) in amount a) and b) used to provide [the R of the disiloxy unit with 5 to 65 % by mole
1 2siO
2/2] and the trimethylsilane oxygen base unit [R of 35 to 95 % by mole
2siO
3/2] resin-linear Organosiloxane block copolymer, and
The wherein step I of at least 95 % by weight) in linear organosiloxane used be incorporated in resin-linear Organosiloxane block copolymer;
II) will step I be derived from) described resin-linear Organosiloxane block copolymer contact the silanol content of resin-linear Organosiloxane block copolymer to be reduced to 5 % by mole or less with alkali thickening agent;
III) optionally, resin-linear Organosiloxane block copolymer is processed further; And
IV) optionally, this organic solvent is removed.
Embodiment 2 relates to the method for embodiment 1, and wherein alkali thickening agent comprises highly basic.
Embodiment 3 relates to the method for embodiment 2, and wherein said highly basic comprises KOH or NaOH.
Embodiment 4 relates to the method for embodiment 1-3, wherein R
2for phenyl.
Embodiment 5 relates to the method for embodiment 1 or 2, wherein R
1for phenyl or methyl.
Embodiment 6 relates to the method for embodiment 1 or 2, and wherein disiloxy unit has formula [(CH
3) (C
6h
5) SiO
2/2].
Embodiment 7 relates to the method for embodiment 1, and wherein said further processing comprises and will derive from Step II) resin-linear organo-siloxane contact with water and remove acetic acid.
Embodiment 8 relates to the method for embodiment 1, and wherein said further processing comprises and will derive from Step II) resin-linear organo-siloxane contact with the end-caps being selected from alcohol, oxime or trialkylsiloxy compound.
Embodiment 9 relates to the method for embodiment 1, wherein replaces described further processing or except described further processing, will derive from Step II) Organosiloxane block copolymer contact with stablizer or super base.
Embodiment 10 relates to the organopolysiloxane segmented copolymer prepared by the method for embodiment 1-9.
Embodiment 11 relates to the organopolysiloxane segmented copolymer of embodiment 10, and wherein organopolysiloxane segmented copolymer is Step II) reaction product.
Embodiment 12 relates to the composition of the organopolysiloxane segmented copolymer comprising embodiment 9.
Embodiment 13 relates to the composition of embodiment 12, and it is curable.
Embodiment 14 relates to the composition of embodiment 12, and it is solid.
Embodiment 15 relates to the cured product of the composition of embodiment 13 or 14.
Embodiment 16 relates to the solid film composition of the composition comprising embodiment 12-15.
Embodiment 17 relates to the solid film composition of embodiment 16, and wherein this solids composition has the transmittance of at least 95%.
Embodiment 18 relates to the LED agent of the composition comprising embodiment 12-17.
Embodiment 19 relates to the linear Organosiloxane block copolymer of resin, and this multipolymer comprises:
Formula [the R of 5 to 65 % by mole
1 2siO
2/2] disiloxy unit,
Formula [the R of 35 to 95 % by mole
2siO
3/2] trimethylsilane oxygen base unit,
5 % by mole or less silanol [≡ SiOH],
The wherein R when occurring at every turn
1be C independently
1to C
30alkyl,
The R when occurring at every turn
2be C independently
1to C
20alkyl, and
Wherein:
Disiloxy unit [R
1 2siO
2/2] with
Each linearity block has average 10 to 400 disiloxy unit [R1
2siO
2/2]
Linearity block arranges,
Trimethylsilane oxygen base unit [R
2siO
3/2] with
Molecular weight is the non-linear block arrangement of at least 500g/mol,
Each linearity block is connected at least one non-linear block, and
The molecular weight of this Organosiloxane block copolymer is at least 5,000g/mol.
Embodiment 20 relates to the Organosiloxane block copolymer of embodiment 19, wherein each R
2for phenyl.
Embodiment 21 relates to the Organosiloxane block copolymer of embodiment 19 or 20, wherein each R
1be methyl or phenyl independently when occurring at every turn.
Embodiment 22 relates to the Organosiloxane block copolymer of embodiment 19 or 20, and wherein disiloxy unit has formula [(CH
3) (C
6h
5) SiO
2/2].
Embodiment 23 relates to the Organosiloxane block copolymer of embodiment 19 or 20, and wherein disiloxy unit has formula [(CH
3)
2siO
2/2].
Embodiment 24 relates to and comprises the Organosiloxane block copolymer of embodiment 20-23 and the curable compositions of organic solvent.
Embodiment
The disclosure is provided for the method for the curable and solids composition prepared some " resin is linear " Organosiloxane block copolymer and comprise " resin is linear " Organosiloxane block copolymer." resin-linear " Organosiloxane block copolymer, provide the advantage of " can reprocess " derived from the curable compositions of these segmented copolymers and solids composition.They can also provide one or more beneficial effects relevant to organosilicon, comprise hydrophobicity, high-temperature stability and moisture resistance/uv-resistance.Finally, this type of resin-linear Organosiloxane block copolymer can also provide the coating with the transmittance being greater than 95%.
Method for the preparation of " resin is linear " Organosiloxane block copolymer of embodiment comprises:
I) make
A) there is the linear organosiloxane of following formula:
R
1 q(E)
(3-q)SiO(R
1 2SiO
2/2)
nSi(E)
(3-q)R
1 q，
Wherein each R
1be C independently when occurring at every turn
1to C
30alkyl,
N is 10 to 400,
Q is 0,1 or 2,
E is the hydrolysable group containing at least one carbon atom, and
B) in its formula, comprise [the R of at least 60 % by mole
2siO
3/2] organosiloxane resins of siloxy units, wherein each R
2be C independently when occurring at every turn
1to C
20alkyl,
React in c) organic solvent;
To form resin-linear Organosiloxane block copolymer;
Wherein select step I) in amount a) and b) used to provide [the R of the disiloxy unit with 5 to 65 % by mole
1 2siO
2/2] and the trimethylsilane oxygen base unit [R of 35 to 95 % by mole
2siO
3/2] resin-linear Organosiloxane block copolymer, and
The wherein step I of at least 95 % by weight) in linear organosiloxane used be incorporated in resin-linear Organosiloxane block copolymer,
II) will step I be derived from) described resin-linear Organosiloxane block copolymer contact to be reduced to by the silanol content of resin-linear Organosiloxane block copolymer 5 % by mole or less (such as, being less than 5 % by mole) with alkali thickening agent;
III) optionally further processing derives from Step II) resin-linear Organosiloxane block copolymer with strengthen package stability and/or optical clarity and/or optionally to deriving from Step II) resin-linear Organosiloxane block copolymer add stablizer or super base; And
IV) optionally, this organic solvent is removed.
The organopolysiloxane of embodiment described herein is " resin-linear " Organosiloxane block copolymer.Organopolysiloxane is for comprising independently selected from [R
3siO
1/2], [R
2siO
2/2], [RSiO
3/2] or [SiO
4/2] polymkeric substance of siloxy units of siloxy units, wherein R can be such as organic group.These siloxy units are usually called M, D, T and Q unit.These siloxy units can by various ways combination with the structure forming ring-type, straight or branched.Depend on number and the type of the siloxy units in organopolysiloxane, chemistry and the physical properties of the polymer architecture of gained change to some extent.Such as, " linearly " organopolysiloxane can mainly comprise D or [R
2siO
2/2] siloxy units, this produces the polydiorganosiloxane as the fluid with different viscosity, and this depends on " polymerization degree " or " dp " indicated by the quantity of the D unit in polydiorganosiloxane." linearly " organopolysiloxane can have the second-order transition temperature (T lower than 25 DEG C
g).When most of siloxy units is selected from T or Q siloxy units, obtain " resin " organopolysiloxane.When main employing T siloxy units prepares organopolysiloxane, the organo-siloxane of gained is commonly referred to " resin " or " silsesquioxane resins ".The amount increasing T or the Q siloxy units in organopolysiloxane can cause polymkeric substance to have the hardness of increase and/or glassy character.Therefore " resin " organopolysiloxane has higher T
gvalue, such as silicone resin usually has and is greater than 40 DEG C, as being greater than 50 DEG C, being greater than 60 DEG C, being greater than 70 DEG C, being greater than 80 DEG C, being greater than 90 DEG C or be greater than the T of 100 DEG C
gvalue.In certain embodiments, the T of silicone resin
gfor about 60 DEG C to about 100 DEG C, 60 DEG C to about 80 DEG C, about 50 DEG C to about 100 DEG C, about 50 DEG C to about 80 DEG C or about 70 DEG C to about 100 DEG C according to appointment.
As used herein, " Organosiloxane block copolymer " or " resin-linear Organosiloxane block copolymer " refers to containing " linearly " D siloxy units and the organopolysiloxane of " resin " T siloxy units that combines with it.In certain embodiments, organosiloxane copolymer relative with " random " multipolymer " block " multipolymer.Therefore, " the resin-linear Organosiloxane block copolymer " of the disclosed embodiments refers to the organopolysiloxane comprising D and T siloxy units, wherein D unit (i.e. [R
1 2siO
2/2] unit) be mainly bonded together to be formed there are average 10 to 400 D unit (such as average about 10 to about 350 D unit in certain embodiments, about 10 to about 300 D unit, about 10 to about 200 D unit, about 10 to about 100 D unit, about 50 to about 400 D unit, about 100 to about 400 D unit, about 150 to about 400 D unit, about 200 to about 400 D unit, about 300 to about 400 D unit, about 50 to about 300 D unit, about 100 to about 300 D unit, about 150 to about 300 D unit, about 200 to about 300 D unit, about 100 to about 150 D unit, about 115 to about 125 D unit, about 90 to about 170 D unit or about 110 to about 140 D unit) polymer chain, it is referred to herein as " linearity block ".
T unit (i.e. [R
2siO
3/2]) mainly bond together in certain embodiments and form branched polymer chains, it is called as " non-linear block ".In certain embodiments, when providing the segmented copolymer of solid form, these a large amount of non-linear block can be assembled further and be formed in " nanometer territory ".In certain embodiments, these nanometer territories form the phase be separated formed with the linearity block with D unit, make to form rich resiniferous phase.
In certain embodiments, non-linear block has at least 500g/mol, as the number-average molecular weight of at least 1000g/mol, at least 2000g/mol, at least 3000g/mol or at least 4000g/mol, or there is about 500g/mol to about 4000g/mol, about 500g/mol to about 3000g/mol, about 500g/mol to about 2000g/mol, about 500g/mol to about 1000g/mol, about 1000g/mol to 2000g/mol, about 1000g/mol to about 1500g/mol, about 1000g/mol to about 1200g/mol, about 1000g/mol to 3000g/mol, about 1000g/mol to about 2500g/mol, about 1000g/mol to about 4000g/mol, the molecular weight of about 2000g/mol to about 3000g/mol or about 2000g/mol to about 4000g/mol.
Organosiloxane block copolymer (as comprise the formula [R of 5 to 65 % by mole
1 2siO
2/2] disiloxy unit and the formula [R of 35 to 95 % by mole
2siO
3/2] those of trimethylsilane oxygen base unit) can by formula [R
1 2siO
2/2]
a[R
2siO
3/2]
brepresent, wherein subscript a and b represents the mole fraction of siloxy units in multipolymer,
A is about 0.05 to about 0.65,
Or about 0.1 to about 0.6,
Or about 0.1 to about 0.4,
B is about 0.35 to about 0.95,
Or about 0.4 to about 0.9,
Or about 0.5 to about 0.85,
Wherein each R
1be C independently when occurring at every turn
1to C
30alkyl, and
Each R
2be C independently when occurring at every turn
1to C
20alkyl.
In certain embodiments, the Organosiloxane block copolymer of embodiment described herein comprises the formula [R of 5 to 65 % by mole
1 2siO
2/2] disiloxy unit, as the formula [R of 10 to 60 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 10 to 50 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 10 to 40 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 10 to 30 % by mole
1 2siO
2/2] disiloxy unit; Or the formula [R of 5 to 50 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 5 to 40 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 5 to 25 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 20 to 60 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 20 to 50 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 20 to 40 % by mole
1 2siO
2/2] disiloxy unit; Or the formula [R of 20 to 30 % by mole
1 2siO
2/2] disiloxy unit.
In certain embodiments, the Organosiloxane block copolymer of embodiment described herein comprises the formula [R of 35 to 95 % by mole
2siO
3/2] trimethylsilane oxygen base unit, as the formula [R of 40 to 90 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 40 to 80 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 40 to 70 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 40 to 60 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 50 to 90 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 50 to 80 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 50 to 70 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 35 to 75 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 35 to 65 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 35 to 55 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 45 to 75 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Or the formula [R of 45 to 65 % by mole
2siO
3/2] trimethylsilane oxygen base unit.
Should be appreciated that the Organosiloxane block copolymer of embodiment described herein can comprise other siloxy units, such as D or the T siloxy units of M siloxy units, Q siloxy units, other uniquenesses (such as, has R
1or R
2outside organic group), prerequisite is the mole fraction that Organosiloxane block copolymer comprises dimethylamino silane oxygen base as described herein and trimethylsilane oxygen base unit.In other words, the mole fraction sum specified by subscript a and b must summation be not necessarily 1.A+b sum can be less than 1 to consider to comprise other siloxy units of trace that may be present in this Organosiloxane block copolymer.Or a+b sum is greater than 0.6, or is greater than 0.7, or is greater than 0.8, or is greater than 0.9.In certain embodiments, a+b sum is about 0.6 to about 0.9, such as about 0.6 to about 0.8, about 0.6 to about 0.7, about 0.7 to about 0.9, about 0.7 to about 0.8 or about 0.8 to about 0.9.
In one embodiment, Organosiloxane block copolymer is substantially by formula [R
1 2siO
2/2] disiloxy unit and formula [R
2siO
3/2] trimethylsilane oxygen base unit composition, also comprise 5 % by mole (such as, being less than 5 % by mole) or less silanol [≡ SiOH] (such as, is less than the silanol of 4 % by mole simultaneously; Be less than the silanol of 3 % by mole; Be less than the silanol of 2 % by mole; Be less than the silanol of 1 % by mole; About 1 to the silanol being less than 5 % by mole; About 2 to the silanol being less than 5 % by mole; About 3 to the silanol being less than 5 % by mole; About 0.5 to the silanol being less than 5 % by mole; The silanol of about 0.5 to about 4 % by mole; The silanol of about 0.5 to about 2 % by mole; The silanol of about 1.5 to about 3.7 % by mole; The silanol of about 2 to about 4 % by mole; Or the silanol of about 0.5 to about 1 % by mole), wherein R
1and R
2as defined herein.Thus, in certain embodiments, a+b sum (when the amount of the dimethylamino silane oxygen base represented with mole fraction in this multipolymer and trimethylsilane oxygen base unit) is greater than 0.95, or is greater than 0.98.
In certain embodiments, resin-linear Organosiloxane block copolymer can also comprise silanol [≡ SiOH], in certain embodiments, it is 5 % by mole or less, the silanol [≡ SiOH] of such as about 0.1 to 5 % by mole, or the silanol of 0.1 to 4 % by mole [≡ SiOH], or 0.1 to 3 % by mole.
Silanol may reside in any siloxy units in Organosiloxane block copolymer.Amount as herein described represents the total amount of the silanol existed in Organosiloxane block copolymer.In certain embodiments, the silanol of major part (be such as greater than 75%, be greater than 80%, be greater than 90%, about 75% to about 90%, about 80% to about 90% or about 75% to about 85%) can be stayed on trimethylsilane oxygen base unit (that is, the resin Composition of segmented copolymer).Although do not wish to be bound by any theory, the silanol that the resin Composition of Organosiloxane block copolymer exists makes segmented copolymer at high temperature to react further or to solidify.
When occurring at every turn, each R in above disiloxy unit
1be C independently
1to C
30alkyl, wherein alkyl can be alkyl, aryl or alkaryl independently.Each R
1can be C independently when occurring at every turn
1to C
30alkyl, or each R
1can be C independently when occurring at every turn
1to C
18alkyl.Or, when occurring at every turn, each R
1can be C independently
1to C
6alkyl, such as methyl, ethyl, propyl group, butyl, amyl group or hexyl.Or, when occurring at every turn, each R
1can be methyl independently.Each R
1can be aryl, such as phenyl, naphthyl or anthryl independently when occurring at every turn.Or, when occurring at every turn, each R
1can be any combination of aforesaid alkyl or aryl independently.Or, when occurring at every turn, each R
1can be phenyl or methyl independently, make in certain embodiments, each disiloxy unit can have two alkyl (such as two methyl); Two aryl (such as two phenyl); Or alkyl (such as methyl) and aryl (such as phenyl).
When occurring at every turn, each R in above trimethylsilane oxygen base unit
2be C independently
1to C
20alkyl (such as C
1to C
10alkyl), wherein alkyl can be alkyl, aryl or alkaryl independently.Each R
2can be C independently when occurring at every turn
1to C
20(such as C
1to C
10alkyl) alkyl, or each R
2can be C independently when occurring at every turn
1to C
8alkyl.Or, when occurring at every turn, each R
2can be C independently
1to C
6alkyl, such as methyl, ethyl, propyl group, butyl, amyl group or hexyl.Or, when occurring at every turn, each R
2can be methyl independently.Each R
2can be aryl, such as phenyl, naphthyl or anthryl independently when occurring at every turn.Or, when occurring at every turn, each R
2can be any combination of aforesaid alkyl or aryl independently.Or, when occurring at every turn, each R
2can be phenyl or methyl independently, make in certain embodiments, each disiloxy unit can have two alkyl (such as two methyl); Two aryl (such as two phenyl); Or alkyl (such as methyl) and aryl (such as phenyl).
As used herein, alkyl also comprises the alkyl of replacement." replacement " general reference is replaced the one or more hydrogen atom in group with substituting group well known by persons skilled in the art and is produced stable compound as described herein as used herein.Suitable substituent example includes but not limited to alkyl, thiazolinyl, alkynyl, cycloalkyl, aryl, alkaryl, hydroxyl, alkoxyl group, aryloxy, carboxyl (i.e. CO
2h), carboxyalkyl, carboxyl aryl, cyano group, nitro etc.The alkyl replaced also comprises the alkyl of halogen substiuted, and wherein halogen can be fluorine, chlorine, bromine or their combination.
In certain embodiments, fluoridated silicone oxygen alkane segmented copolymer also can be prepared via method as herein described, make the U.S. Provisional Patent Application No.61/608 that the fluoridated silicone oxygen alkane segmented copolymer of gained and on March 9th, 2012 submit to, 732 is identical with those described in PCT application No.PCT/US2013/027904, whole disclosures of two parts of patent applications are incorporated to way of reference, as herein complete illustrate.
Formula [the R of Organosiloxane block copolymer is described as being used for herein
1 2siO
2/2]
a[R
2siO
3/2]
band use the relational expression of mole fraction not indicate dimethylamino silane oxygen base [R
1 2siO
2/2] and trimethylsilane oxygen base [R
2siO
3/2] unit structural order in the copolymer.On the contrary, this formula is intended to, according to the mole fraction described herein by subscript a and b, provide representation easily for describing the relative quantity of these two kinds of unit in this multipolymer.Mole fraction and the silanol content of the various siloxy units in Organosiloxane block copolymer of the present invention can easily pass through
29si NMR technical measurement.
The Organosiloxane block copolymer of embodiment described herein has the weight-average molecular weight (M of at least 20,000g/mol
w) or at least 40, the weight-average molecular weight of 000g/mol or the weight-average molecular weight of at least 50,000g/mol or the weight-average molecular weight or at least 70 of at least 60,000g/mol, the weight-average molecular weight of 000g/mol or at least 80,000g/mol weight-average molecular weight.In certain embodiments, the Organosiloxane block copolymer of embodiment described herein has the weight-average molecular weight (M of about 20,000g/mol to about 250,000g/mol or about 100,000g/mol to about 250,000g/mol
w), or the weight-average molecular weight of about 40,000g/mol to about 100,000g/mol or about 50,000g/mol is to about 100, the weight-average molecular weight of 000g/mol or about 50,000g/mol to about 80,000g/mol weight-average molecular weight or about 50,000g/mol is to about 70, the weight-average molecular weight of 000g/mol or about 50,000g/mol to about 60,000g/mol weight-average molecular weight.In certain embodiments, the Organosiloxane block copolymer of embodiment described herein has about 15, and 000 to about 50,000g/mol, about 15,000 to about 30,000g/mol, about 20, and 000 to about 30,000g/mol or about 20, the number-average molecular weight (M of 000 to about 25,000g/mol
n).Molecular-weight average can easily measure by gel permeation chromatography (GPC) technology.
In certain embodiments, the structural order of dimethylamino silane oxygen base and trimethylsilane oxygen base unit can further describe as follows: disiloxy unit [R
1 2siO
2/2] with linearity block arrangement, each linearity block has average 10 to 400 disiloxy unit [R
1 2siO
2/2], and trimethylsilane oxygen base unit [R
2siO
3/2] with molecular weight be at least 500g/mol non-linear block arrangement.Each linearity block is connected at least one non-linear block in this segmented copolymer.In addition, the non-linear block of at least 30% is cross-linked to each other, or the non-linear block of at least 40% is cross-linked to each other, or the non-linear block of at least 50% is cross-linked to each other, wherein provide herein in order to represent all per-cents of crosslinked non-linear block per-cent all by weight percentage.
In other embodiments, the non-linear block of about 30% to about 80% is cross-linked to each other; The non-linear block of about 30% to about 70% is cross-linked to each other; The non-linear block of about 30% to about 60% is cross-linked to each other; The non-linear block of about 30% to about 50% is cross-linked to each other; The non-linear block of about 30% to about 40% is cross-linked to each other; The non-linear block of about 40% to about 80% is cross-linked to each other; The non-linear block of about 40% to about 70% is cross-linked to each other; The non-linear block of about 40% to about 60% is cross-linked to each other; The non-linear block of about 40% to about 50% is cross-linked to each other; The non-linear block of about 50% to about 80% is cross-linked to each other; The non-linear block of about 50% to about 70% is cross-linked to each other; The non-linear block of about 50% to about 60% is cross-linked to each other; The non-linear block of about 60% to about 80% is cross-linked to each other; Or the non-linear block of about 60% to about 70% is cross-linked to each other.
The crosslinked of non-linear block realizes by number of chemical mechanism and/or part.Such as, the crosslinked of the non-linear block in this segmented copolymer can be caused by the residual silane alcohol groups condensation existed in the non-linear block of this multipolymer.The crosslinked of non-linear block in this segmented copolymer also can occur between component and non-linear block at " free resin ".Owing to using excessive organosiloxane resins in the process of this segmented copolymer of preparation, " free resin " component can be present in block copolymer composition.This free resin component can be cross-linked by the condensation of residual silane alcohol groups existed on non-linear block and on free resin with non-linear block.This free resin provides crosslinked by reacting with the lower molecular weight compound of adding as linking agent, as described herein.Free resin content when it is present can be about 10 % by weight to about 20 % by weight of the Organosiloxane block copolymer of embodiment described herein, about 15 % by weight to about 20 % by weight of the Organosiloxane block copolymer of such as embodiment described herein.
In certain embodiments, some compound can be added in the preparation process of segmented copolymer, such as, as linking agent.These compounds can be included in the forming process of segmented copolymer (as discussed herein (Step II)) add there is formula R
5 qsiX
4-qorganosilane, wherein R
5for C
1to C
8alkyl or C
1to C
8the alkyl of halogen substiuted; X is hydrolysable group; And q is 0,1 or 2.R
5for C
1to C
8alkyl or C
1to C
8the alkyl of halogen substiuted, or R
5for C
1to C
8alkyl, or phenyl, or R
5for the combination of methyl, ethyl or methyl and ethyl.X is any hydrolysable group E, or X can be oximido, acetoxyl group, halogen atom, hydroxyl (OH) or alkoxyl group.
In one embodiment, there is formula R
5 qsiX
4-qorganosilane be alkyl triacetoxysilane, such as methyl triacetoxysilane, ethyltriacetoxysilane or both combinations.Commercially available representative alkyl triacetoxysilane comprises ETS-900 (available Dow Corning Corporation (Dow Corning Corp., Midland, MI)).
When in Step II) period is when adding, and has formula R
5 qsiX
4-qthe amount of organosilane can change to some extent, but in certain embodiments based on the amount of organosiloxane resins used in the method.Such as, the amount of silane used can provide organosilane to be the molar stoichiometric of 2 to 15 % by mole with the ratio of the Si mole number in organosiloxane resins, and such as organosilane is 2 to 10 % by mole with the ratio of the Si mole number in organosiloxane resins; Organosilane is 5 to 15 % by mole with the ratio of the Si mole number in organosiloxane resins; Organosilane is 2 to 5 % by mole with the ratio of the Si mole number in organosiloxane resins; Organosilane is 10 to 15 % by mole with the ratio of the Si mole number in organosiloxane resins; Organosilane is 5 to 10 % by mole with the ratio of the Si mole number in organosiloxane resins; Or organosilane is 2 to 12 % by mole with the ratio of the Si mole number in organosiloxane resins.In addition, in certain embodiments, rate-determining steps II) in add there is formula R
5 qsiX
4-qthe amount of organosilane, to guarantee that stoichiometry can not consume the whole silanol in Organosiloxane block copolymer.In one embodiment, to Step II) in the amount of organosilane used select, with the Organosiloxane block copolymer of providing package containing the silanol [≡ SiOH] of 5 % by mole or less (being such as less than 5 % by mole).
Other suitable non-limiting organosilanes that such as can be used as linking agent comprise: methyl three (methyl ethyl ketone oximido) silane (MTO), methyl triacetoxysilane, ethyltriacetoxysilane, four acetoxysilanes, four oximino silanes, dimethyldiacetoxy silane, dimethyl two oximino silane and methyl three (methyl ketoxime base) silane.
The crosslinked siloxane bond ≡ Si-O-Si ≡ that can mainly be produced by silanol condensation in segmented copolymer, as discussed herein.
Cross-linking amount in this segmented copolymer is estimated by the molecular-weight average measuring this segmented copolymer, as used GPC technology.In certain embodiments, cross-linked block copolymer will increase its molecular-weight average.Thus, the selection (chain length namely indicated by its polymerization degree) of the molecular-weight average of given segmented copolymer, linearly siloxy-component and the molecular weight (its selection being mainly exposed for the organosiloxane resins preparing segmented copolymer controls) of non-linear block, can estimate crosslinking degree.
In certain embodiments, the solids composition comprising the resin-linear Organosiloxane block copolymer of embodiments more described herein also comprises super basic catalyst.See the U.S. Provisional Application No.61/570 that the PCT application No.PCT/US2012/069701 and 2012 submitted in such as on December 14th, 2012 submits 14, on December, 477, their full text is incorporated to way of reference, as this paper is complete illustrate.
In certain embodiments, the solids composition comprising the resin-linear Organosiloxane block copolymer of embodiments more described herein also comprises stablizer.See the U.S. Provisional Application No.61/566 that the PCT application No.PCT/US2012/067334 and 2011 submitted in such as on November 30th, 2012 submits 2, on December, 031, their full text is incorporated to way of reference, as this paper is complete illustrate.
The disclosure also provides curable composition, and it comprises:
A) Organosiloxane block copolymer as described herein, and the stablizer as described herein combined with it in certain embodiments or super base, and
B) organic solvent.
In certain embodiments, organic solvent is aromatic solvent, such as benzene,toluene,xylene or its combination.
In one embodiment, this curable composition can also comprise organosiloxane resins (not being such as the free resin of a segmented copolymer part).The organosiloxane resins be present in these compositions is the identical organosiloxane resins for the preparation of Organosiloxane block copolymer as described herein in certain embodiments.
The amount of the Organosiloxane block copolymer in curable compositions, organic solvent and optional organosiloxane resins can change to some extent.Curable compositions can comprise:
The Organosiloxane block copolymer as described herein (such as 40 to 70 % by weight, 40 to 60 % by weight, 40 to 50 % by weight) of 40 to 80 % by weight;
The organic solvent (such as 10 to 70 % by weight, 10 to 60 % by weight, 10 to 50 % by weight, 10 to 40 % by weight, 10 to 30 % by weight, 10 to 20 % by weight, 20 to 80 % by weight, 30 to 80 % by weight, 40 to 80 % by weight, 50 to 80 % by weight, 60 to 80 % by weight or 70 to 80 % by weight) of 10 to 80 % by weight; And
The organosiloxane resins (such as 5 to 30 % by weight, 5 to 20 % by weight, 5 to 10 % by weight, 10 to 40 % by weight, 10 to 30 % by weight, 10 to 20 % by weight, 20 to 40 % by weight or 30 to 40 % by weight) of 5 to 40 % by weight;
% by weight sum of these components is made to be no more than 100%.In one embodiment, curable compositions is made up of Organosiloxane block copolymer as described herein, organic solvent and organosiloxane resins substantially.In certain embodiments, these components % by weight summation be 100% or close to 100%.
Solids composition containing this resin-linear Organosiloxane block copolymer is prepared by being removed from curable organosiloxane block copolymer composition as herein described by solvent.Solvent removes by any known processing technology.In one embodiment, form the film of the curable compositions containing this Organosiloxane block copolymer, and allow solvent evaporate from film.Film is made to stand high temperature and/or decompression can remove and formed with follow-up solid curable composition by accelerated solvent.Or, banded or pellet form solids composition can be provided by forcing machine to remove solvent by this curable compositions.Also can be used in the painting work that antiadhesion barrier carries out, as in slit coating, knife-over-roll coating (knife over roll), rod painting or intaglio plate coating.In addition, volume to volume painting work can be used for preparing solid film.In painting work, the means of continuous tunnel furnace (conveyer oven) or other heating and discharge solution can be obtained final solid film for expelling solvent.
Although do not wish to be bound by any theory, but likely, when forming the solids composition of segmented copolymer, the structural order of the disiloxy unit in Organosiloxane block copolymer as described herein and trimethylsilane oxygen base unit can be the physical property profile that multipolymer provides some uniqueness.Such as, the structural order of the disiloxy unit in this multipolymer and trimethylsilane oxygen base unit can provide solid cladding, this solid cladding allow high visible transmittance (such as under the wavelength of more than 350nm at least 85% transmittance, at least 90% transmittance, the transmittance of at least 95%, the transmittance of at least 99% or 100% transmittance).This structural order also can make this Organosiloxane block copolymer to flow and the solidification when heating, and at room temperature keeps stable.Also available lamination is processed them.These character can be used for for various electronic products provides coating to improve weathering resistance and weather resistance, and provide energy-conservation low cost and easy operation simultaneously.
The disclosure also relates to the solid form of above-mentioned Organosiloxane block copolymer and comes from the solids composition of the curable compositions as herein described comprising described Organosiloxane block copolymer.Thus, the disclosure provides Organosiloxane block copolymer, and it comprises:
Formula [the R of 5 to 65 % by mole
1 2siO
2/2] disiloxy unit,
Formula [the R of 35 to 95 % by mole
2siO
3/2] trimethylsilane oxygen base unit,
The silanol [≡ SiOH] of 5 % by mole or less (being such as less than the silanol of 5 % by mole);
Wherein:
Each R
1be C independently when occurring at every turn
1to C
30alkyl,
Each R
2be C independently when occurring at every turn
1to C
20alkyl;
Wherein:
Disiloxy unit [R
1 2siO
2/2] with linearity block arrangement, each linearity block has average 10 to 400 disiloxy unit [R
1 2siO
2/2],
Trimethylsilane oxygen base unit [R
2siO
3/2] to have the non-linear block arrangement of the molecular weight of at least 500g/mol, the non-linear block of at least 30% is cross-linked to each other and mainly flocks together in nanometer territory,
Each linearity block is connected at least one non-linear block; And
Organosiloxane block copolymer has the weight-average molecular weight of at least 20,000g/mol, and is solid at 25 DEG C.
In certain embodiments, contained in solid form and solids composition Organosiloxane block copolymer comprises the formula [R of 5 to 65 % by mole
1 2siO
2/2] disiloxy unit, as the formula [R of 10 to 60 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 10 to 50 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 10 to 40 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 10 to 30 % by mole
1 2siO
2/2] disiloxy unit; Or the formula [R of 5 to 50 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 5 to 40 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 5 to 25 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 20 to 60 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 20 to 50 % by mole
1 2siO
2/2] disiloxy unit; Formula [the R of 20 to 40 % by mole
1 2siO
2/2] disiloxy unit; Or the formula [R of 20 to 30 % by mole
1 2siO
2/2] disiloxy unit.
In certain embodiments, contained in solid form and solids composition Organosiloxane block copolymer comprises the formula [R of 35 to 95 % by mole
2siO
3/2] trimethylsilane oxygen base unit, as the formula [R of 40 to 90 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 40 to 80 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 40 to 70 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 40 to 60 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 50 to 90 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 50 to 80 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 50 to 70 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 35 to 75 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 35 to 65 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 35 to 55 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Formula [the R of 45 to 75 % by mole
2siO
3/2] trimethylsilane oxygen base unit; Or the formula [R of 45 to 65 % by mole
2siO
3/2] trimethylsilane oxygen base unit.
In certain embodiments, contained in solid form and solids composition Organosiloxane block copolymer comprises 5 % by mole (being such as less than 5 % by mole) or less silanol [≡ SiOH] (is such as less than the silanol of 4 % by mole; Be less than the silanol of 3 % by mole; Be less than the silanol of 2 % by mole; Be less than the silanol of 1 % by mole; About 1 to the silanol being less than 5 % by mole; About 2 to the silanol being less than 5 % by mole; About 3 to the silanol being less than 5 % by mole; About 0.5 to the silanol being less than 5 % by mole; The silanol of about 0.5 to about 4 % by mole; The silanol of about 0.5 to about 2 % by mole; The silanol of about 1.5 to about 3.7 % by mole; The silanol of about 2 to about 4 % by mole; Or the silanol of about 0.5 to about 1 % by mole).
In certain embodiments, the disiloxy unit [R in contained in solid form and solids composition Organosiloxane block copolymer
1 2siO
2/2] with linearity block arrangement, described linearity block has average 10 to 400 disiloxy unit, such as average about 10 to about 350 disiloxy unit; About 10 to about 300 disiloxy unit; About 10 to about 200 disiloxy unit; About 10 to about 100 disiloxy unit; About 50 to about 400 disiloxy unit; About 100 to about 400 disiloxy unit; About 150 to about 400 disiloxy unit; About 200 to about 400 disiloxy unit; About 300 to about 400 disiloxy unit; About 50 to about 300 disiloxy unit; About 100 to about 300 disiloxy unit; About 150 to about 300 disiloxy unit; About 200 to about 300 disiloxy unit; About 100 to about 150 disiloxy unit; About 115 to about 125 disiloxy unit; About 90 to about 170 disiloxy unit or about 110 to about 140 disiloxy unit.
In certain embodiments, non-linear block in Organosiloxane block copolymer contained in solid form and solids composition has at least 500g/mol, as the number-average molecular weight of at least 1000g/mol, at least 2000g/mol, at least 3000g/mol or at least 4000g/mol, or there is about 500g/mol to about 4000g/mol, about 500g/mol to about 3000g/mol, about 500g/mol to about 2000g/mol, about 500g/mol to about 1000g/mol, about 1000g/mol to 2000g/mol, about 1000g/mol to about 1500g/mol, about 1000g/mol to about 1200g/mol, about 1000g/mol to 3000g/mol, about 1000g/mol to about 2500g/mol, about 1000g/mol to about 4000g/mol, the molecular weight of about 2000g/mol to about 3000g/mol or about 2000g/mol to about 4000g/mol.
In certain embodiments, in Organosiloxane block copolymer contained in solid form and solids composition, the non-linear block of at least 30% is cross-linked to each other, and the non-linear block as at least 40% is cross-linked to each other; The non-linear block of at least 50% is cross-linked to each other; The non-linear block of at least 60% is cross-linked to each other; The non-linear block of at least 70% is cross-linked to each other; Or the non-linear block of at least 80% is cross-linked to each other.In other embodiments, the non-linear block of about 30% to about 80% is cross-linked to each other; The non-linear block of about 30% to about 70% is cross-linked to each other; The non-linear block of about 30% to about 60% is cross-linked to each other; The non-linear block of about 30% to about 50% is cross-linked to each other; The non-linear block of about 30% to about 40% is cross-linked to each other; The non-linear block of about 40% to about 80% is cross-linked to each other; The non-linear block of about 40% to about 70% is cross-linked to each other; The non-linear block of about 40% to about 60% is cross-linked to each other; The non-linear block of about 40% to about 50% is cross-linked to each other; The non-linear block of about 50% to about 80% is cross-linked to each other; The non-linear block of about 50% to about 70% is cross-linked to each other; The non-linear block of about 55% to about 70% is cross-linked to each other; The non-linear block of about 50% to about 60% is cross-linked to each other; The non-linear block of about 60% to about 80% is cross-linked to each other; Or the non-linear block of about 60% to about 70% is cross-linked to each other.
In certain embodiments, contained in solid form and solids composition Organosiloxane block copolymer has the weight-average molecular weight (M of at least 20,000g/mol
w) or at least 40, the weight-average molecular weight of 000g/mol or the weight-average molecular weight of at least 50,000g/mol or the weight-average molecular weight or at least 70 of at least 60,000g/mol, the weight-average molecular weight of 000g/mol or at least 80,000g/mol weight-average molecular weight.In certain embodiments, contained in solid form and solids composition Organosiloxane block copolymer has the weight-average molecular weight (M of about 20,000g/mol to about 250,000g/mol or about 100,000g/mol to about 250,000g/mol
w), or the weight-average molecular weight of about 40,000g/mol to about 100,000g/mol or about 50,000g/mol is to about 100, the weight-average molecular weight of 000g/mol or about 50,000g/mol to about 80,000g/mol weight-average molecular weight or about 50,000g/mol is to about 70, the weight-average molecular weight of 000g/mol or about 50,000g/mol to about 60,000g/mol weight-average molecular weight.In certain embodiments, the Organosiloxane block copolymer of embodiment described herein has about 15, and 000 to about 50,000g/mol, about 15,000 to about 30,000g/mol, about 20, and 000 to about 30,000g/mol or about 20, the number-average molecular weight (M of 000 to about 25,000g/mol
n).
In certain embodiments, aforementioned organic silicon oxygen alkane segmented copolymer is such as separated in the following manner in solid form: the film of the solution of cast block copolymer in organic solvent (as benzene,toluene,xylene or their combination), and solvent is evaporated.Under these conditions, aforementioned organic silicon oxygen alkane segmented copolymer can be provided containing the solution of having an appointment in the organic solvent of 50 % by weight to about 80 % by weight solid substances such as about 60 % by weight to about 80 % by weight, about 70 % by weight to about 80 % by weight or about 75 % by weight to about 80 % by weight solid substance.In certain embodiments, solvent is toluene.In certain embodiments, this type of solution can have at the 25 DEG C about 1500 centistokes viscosity to about 4000 centistokes, such as at 25 DEG C about 1500 centistokes to about 3000 centistokes, about 2000 centistokes to about 4000 centistokes or about 2000 centistokes to the viscosity of about 3000 centistokes.
In drying or when forming solid, the non-linear block of this segmented copolymer flocks together further and is formed in " nanometer territory ".As used herein, " mainly assembling " non-linear block meaning major part (be such as greater than 50%, be greater than 60%, be greater than 75%, be greater than 80%, be greater than 90%, about 75% to about 90%, about 80% to about 90% or about 75% to about 85%) Organosiloxane block copolymer is present in some region of solids composition, and these regions are referred to herein as in " nanometer territory ".As used herein, " nanometer territory " refers to those phase regions in solid block copolymer composition, and described phase region is separated in solid block copolymer composition, and at least one dimension is 1 to 100 nanometer.This nanometer territory can change to some extent at vpg connection, as long as at least one dimension in this nanometer territory is 1 to 100 nanometer.Thus, the shape in this nanometer territory can be regular or irregular.This nanometer territory can be spherical, tubular, and is stratiform shape in some cases.
In yet another embodiment, solid organosilicone segmented copolymer as described herein contains first-phase and inconsistent second-phase, and this first-phase is mainly containing disiloxy unit [R as herein defined
1 2siO
2/2], this second-phase is mainly containing trimethylsilane oxygen base unit [R as herein defined
2siO
3/2], non-linear block is fully gathered into the inconsistent nanometer territory with first-phase.
When solids composition is formed by the curable compositions (it can also contain organosiloxane resins) of Organosiloxane block copolymer as described herein, this organosiloxane resins also can mainly be assembled in nanometer territory.
The structural order of the disiloxy unit in disclosure solid block copolymer and trimethylsilane oxygen base unit and the sign in nanometer territory, some analytical technology available clearly measures, as transmission electron microscope (TEM) technology, atomic force microscopy (AFM), small-angle neutron scattering, small angle X ray scattering and scanning electron microscopy.
Or the structural order of the disiloxy unit in this segmented copolymer and trimethylsilane oxygen base unit and the formation in nanometer territory, imply by characterizing some physical properties deriving from the coating of Organosiloxane block copolymer of the present invention.Such as, organosiloxane copolymer of the present invention can provide visible light transmittance rate to be greater than the coating of 95%.Those skilled in the art recognize that, only when visible ray by a kind of like this medium and not can be greater than particle (or the as used herein territory) diffraction of 150 nanometers by size, this optical clarity is only possible (instead of refractive index match of two-phase).When granularity or territory reduce further, this optical clarity can improve further.Thus, the coating coming from organosiloxane copolymer of the present invention can have the visible light transmittance rate of at least 95%, the visible light transmittance rate of such as at least 96%, at least 97%, at least 98%, at least 99% or 100%.As used herein, term " visible ray " comprises the light of more than 350nm wavelength.
The advantage of resin-linear organopolysiloxane segmented copolymer of the present invention is that they can process for several times, because processing temperature (T
processing) be less than the temperature (T finally solidified needed for this Organosiloxane block copolymer
solidification), that is, T
processing<T
solidification.But, when employing is greater than T
solidificationt
processingtime, organosiloxane copolymer is curable and realize high-temperature stability.Thus, resin-linear organopolysiloxane segmented copolymer of the present invention provide the remarkable advantage of " can reprocess " and can be relevant to organosilicon beneficial effect, such as hydrophobicity, high-temperature stability, moisture resistance/uv-resistance.
In one embodiment, the solids composition of Organosiloxane block copolymer can be regarded as " melt-processable ".In certain embodiments, solids composition (coating such as formed by the film of the solution containing Organosiloxane block copolymer) at high temperature (namely time " melting ") show fluid behavior." melt-processable " feature of the solids composition of Organosiloxane block copolymer was monitored by " melt-flow temperature " (namely when solids composition shows liquid behavior) measuring solids composition.Melt-flow temperature specifically measures by measuring temperature variant storage modulus (G '), out-of-phase modulus (G ") and loss tangent (tan δ) with commercial instruments.Such as, commercially available rheometer (the such as ARES-RDA of TA instrument company (TA Instruments), it has 2KSTD standard ball pivot spring transverter, with forced convection oven) can be used for measuring temperature variant storage modulus (G '), out-of-phase modulus (G ") and loss tangent.Test specimen (such as wide 8mm, thick 1mm) can be carried between parallel plate and also measure with small strain oscillatory rheometer, with 2 DEG C/min, temperature be risen to 300 DEG C (frequency is for 1Hz) from 25 DEG C simultaneously.Can be the inflection temperature (be designated as FLOW) of G ' when declining by flowing initial calculation, viscosity when 120 DEG C be reported as the tolerance to melt-processible, and solidification initial calculation is the starting temperature (be designated as CURE) of G ' when rising.The FLOW of solids composition also can be associated with the second-order transition temperature of the non-linear segment (such as resin Composition) in Organosiloxane block copolymer.
In certain embodiments, loss tangent=1 is about 3 to about 5 hours at 150 DEG C, be such as about 3 to about 5 minutes at 150 DEG C, at 150 DEG C for about 10 to about 15 minutes, at 150 DEG C for about 10 to about 12 minutes, at 150 DEG C for about 8 to about 10 minutes, at 150 DEG C for about 30 minutes to about 2.5 hours, at 150 DEG C for about 1 is little up to about 4 hours or be about 2.5 little of about 5 hours at 150 DEG C.
In an other embodiment, this solids composition can be characterized by has 25 DEG C to 200 DEG C, or 25 DEG C to 160 DEG C, or the melt-flow temperature of 50 DEG C to 160 DEG C.
It is believed that melt-processible beneficial effect makes the solids composition of Organosiloxane block copolymer to be formed on device after primary coat or solid can lower than T
solidificationtemperature under again flow around device architecture.This feature is very favourable for the various electronic installation of encapsulation.
In one embodiment, the solids composition of Organosiloxane block copolymer can be regarded as " curable ".In certain embodiments, by solidifying segmented copolymer further, can there is other change in physical in solids composition (coating such as formed by the film of the solution containing Organosiloxane block copolymer).As discussed herein, Organosiloxane block copolymer of the present invention contains a certain amount of silanol.Such as, it is possible that there are these silanol to make that there is further reactivity, curing mechanism on segmented copolymer.During solidification, the physical properties of solids composition can change further.
Or " melt processable " of the solids composition of Organosiloxane block copolymer, state of cure and/or solidification rate are determined by the flow measurement under differing temps.
Solids composition containing this Organosiloxane block copolymer can have the out-of-phase modulus (G ") of the storage modulus (G ') of 0.01MPa to 500MPa and 0.001MPa to 250MPa at 25 DEG C; or at 25 DEG C, have the storage modulus (G ') of 0.1MPa to 250MPa and 0.01MPa to 125MPa out-of-phase modulus (G "), or at 25 DEG C, have the out-of-phase modulus (G ") of the storage modulus (G ') of 0.1MPa to 200MPa and 0.01MPa to 100MPa.
Solids composition containing Organosiloxane block copolymer has 10Pa to 500 at 120 DEG C, the storage modulus of 000Pa (G ') and 10Pa to 500, the out-of-phase modulus of 000Pa (G "); or at 120 DEG C, there is 20Pa to 250; storage modulus of 000Pa (G ') and 20Pa to 250; out-of-phase modulus of 000Pa (G "), or at 120 DEG C, there is 30Pa to 200, the out-of-phase modulus of the storage modulus of 000Pa (G ') and 30Pa to 200,000Pa (G ").
Solids composition containing this Organosiloxane block copolymer can have 10Pa to 100 at 200 DEG C, the storage modulus of 000Pa (G ') and 5Pa to 80, the out-of-phase modulus of 000Pa (G "); or can 20Pa to 75 be had at 200 DEG C; the storage modulus of 000Pa (G ') and 10Pa to 65; out-of-phase modulus of 000Pa (G "), or can 30Pa to 50 be had at 200 DEG C, the out-of-phase modulus of the storage modulus of 000Pa (G ') and 15Pa to 40,000Pa (G ").
This solids composition also by some physical properties as tensile strength and extension at break per-cent characterize.The solids composition of the present invention coming from above-mentioned Organosiloxane block copolymer can have and is greater than 1.0MPa or is greater than 1.5MPa or is greater than the initial tensile strength of 2MPa.In certain embodiments, this solids composition can have the initial tensile strength of 1.0MPa to about 10MPa such as about 1.5MPa to about 10MPa, about 2MPa to about 10MPa, about 5MPa to about 10MPa or about 7MPa to about 10MPa.The solids composition of the present invention coming from above-mentioned Organosiloxane block copolymer can have be greater than 40% or be greater than 50% or be greater than 75% initial collapse (or breaking) elongation per-cent.In certain embodiments, this solids composition can have about 20% to about 90%, and such as about 25% to about 50%, about 20% to about 60%, about 40% to about 60%, about 40% to about 50% or fracture (breaking) the elongation per-cent of about 75% to about 90%.Tensile strength used herein and extension at break per-cent are measured according to ASTM D412.
The disclosure is also provided for the method preparing some resin-linear Organosiloxane block copolymer, and the method comprises:
I) make
A) there is the linear organosiloxane of following formula:
R
1 q(E)
(3-q)SiO(R
1 2SiO
2/2)
nSi(E)
(3-q)R
1 q，
Wherein each R
1be C independently when occurring at every turn
1to C
30alkyl,
N is 10 to 400,
Q is 0,1 or 2,
E is the hydrolysable group containing at least one carbon atom, and
B) in its formula, comprise [the R of at least 60 % by mole
2siO
3/2] organosiloxane resins of siloxy units, wherein each R
2be C independently when occurring at every turn
1to C
20alkyl,
React in c) organic solvent;
To form resin-linear Organosiloxane block copolymer;
Wherein select step I) in amount a) and b) used to provide [the R of the disiloxy unit with 5 to 65 % by mole
1 2siO
2/2] and the trimethylsilane oxygen base unit [R of 35 to 95 % by mole
2siO
3/2] resin-linear Organosiloxane block copolymer, and
The wherein step I of at least 95 % by weight) in linear organosiloxane used be incorporated in resin-linear Organosiloxane block copolymer,
II) will step I be derived from) described resin-linear Organosiloxane block copolymer contact to be reduced to by the silanol content of resin-linear Organosiloxane block copolymer 5 % by mole or less (such as, being less than 5 % by mole) with alkali thickening agent;
III) optionally further processing derives from Step II) resin-linear Organosiloxane block copolymer with strengthen package stability and/or optical clarity and/or optionally to deriving from Step II) resin-linear Organosiloxane block copolymer add stablizer or super base; And
IV) optionally, this organic solvent is removed.
Step I in the method) comprise and making:
A) there is the linear organosiloxane of following formula:
R
1 q(E)
(3-q)SiO(R
1 2SiO
2/2)
nSi(E)
(3-q)R
1 q，
Wherein each R
1be C independently when occurring at every turn
1to C
30alkyl,
N is 10 to 400,
Q is 0,1 or 2,
E is the hydrolysable group containing at least one carbon atom; With
B) in its formula, comprise [the R of at least 60 % by mole
2siO
3/2] organosiloxane resins of siloxy units, wherein each R
2be C independently when occurring at every turn
1to C
20alkyl.
The step I of the method) reaction can roughly represent according to following schematic diagram:
OH group wherein on linear organosiloxane and the hydrolysable group (E) on organosiloxane resins react, to form resin-linear Organosiloxane block copolymer and H-(E) compound.Step I) in reaction can be regarded as between organosiloxane resins and linear organosiloxane condensation reaction.
linear organosiloxane
The step I of the method) in component a) for having formula R
1 q(E)
(3-q)siO (R
1 2siO
2/2)
nsi (E)
(3- q)r
1 qlinear organosiloxane, wherein each R
1be C independently when occurring at every turn
1to C
30alkyl, subscript " n " can be regarded as the polymerization degree (dp) of linear organosiloxane and can change (such as average about 10 to about 400 D unit between 10 to 400, about 10 to about 300 D unit, about 10 to about 200 D unit, about 10 to about 100 D unit, about 50 to about 400 D unit, about 100 to about 400 D unit, about 150 to about 400 D unit, about 200 to about 400 D unit, about 300 to about 400 D unit, about 50 to about 300 D unit, about 100 to about 300 D unit, about 150 to about 300 D unit, about 200 to about 300 D unit, about 100 to about 150 D unit, about 115 to about 125 D unit, about 90 to about 170 D unit or about 110 to about 140 D unit), subscript " 1 " can be 0,1 or 2, and E is the hydrolysable group containing at least one carbon atom.Although component a) is described to have formula R
1 q(E)
(3- q)siO (R
1 2siO
2/2)
nsi (E)
(3-q)r
1 qlinear organosiloxane, but those skilled in the art recognizes, can by a certain amount of alternative siloxy units (as T [R
1siO
3/2] siloxy units) be incorporated in component linear organosiloxane a).Therefore, organo-siloxane is because having most of D [R
1 2siO
2/2] siloxy units and can be regarded as " mainly " be linear.In addition, as component linear organosiloxane a) can be the combination of several linear organosiloxane.In addition, silanol can be comprised as component linear organosiloxane a).In certain embodiments, the silanol of about 0.5 to about 5 % by mole is comprised, the silanol of such as about 1 % by mole to about 3 % by mole, about 1 % by mole to about 2 % by mole or about 1 % by mole to about 1.5 % by mole as component linear organosiloxane a).
When occurring at every turn, each R in above linear organosiloxane
1be C independently
1to C
30alkyl, wherein alkyl can be alkyl, aryl or alkaryl independently.Each R
1can be C independently when occurring at every turn
1to C
30alkyl, or each R
1can be C independently when occurring at every turn
1to C
18alkyl.Or, when occurring at every turn, each R
1can be C independently
1to C
6alkyl, such as methyl, ethyl, propyl group, butyl, amyl group or hexyl.Or, when occurring at every turn, each R
1can be methyl independently.Each R
1can be aryl, such as phenyl, naphthyl or anthryl independently when occurring at every turn.Or, when occurring at every turn, each R
1can be any combination of aforesaid alkyl or aryl independently.Or, when occurring at every turn, each R
1can be phenyl or methyl independently, make in certain embodiments, each disiloxy unit can have two alkyl (such as two methyl); Two aryl (such as two phenyl); Or alkyl (such as methyl) and aryl (such as phenyl).
E can be selected from any containing at least one carbon atom (such as one to ten carbon atom; One to five carbon atom; One to four carbon atom; Or one to three carbon atom) hydrolysable group.In certain embodiments, E is selected from oximido, epoxy group(ing), carboxyl, amino, amide group or their combination.Or E can have formula R
1c (=O) O-, R
1 2c=N-O-or R
4c=N-O-, wherein R
1as defined herein, and R
4for alkyl.In one embodiment, E is H
3cC (=O) O-(acetoxyl group).In one embodiment, E is (CH
3) (CH
3cH
2) C=N-O-(methyl ethyl ketone oximido).
In one embodiment, this linear organosiloxane has following formula:
(CH
3)
q(E)
(3-q)siO [(CH
3)
2siO
2/2)]
nsi (E)
(3-q)(CH
3)
q, wherein E, n and q are as hereinbefore defined.
In one embodiment, this linear organosiloxane has following formula:
(CH
3)
q(E)
(3-q)siO [(CH
3) (C
6h
5) SiO
2/2)]
nsi (E)
(3-q)(CH
3)
q, wherein E, n and q are as hereinbefore defined.
Known for the preparation of the method being suitable as component linear organosiloxane a).In certain embodiments, silanol stopped polydiorganosiloxane can be made to react with " end-blocking " compound of such as alkyl triacetoxysilane or dialkyl group ketoxime.Can adjust the stoichiometry of this end capping, come with some on this organosiloxane resins but not all silanol is reacted to make to add enough end-caps.In certain embodiments, this stoichiometry of adjustable is to react with the substantially all silanol on this organosiloxane resins.In certain embodiments, the silanol on every mole of polydiorganosiloxane uses one mole of this end-caps.Or, can use a little molar excess as 1 to 10% excessive end-caps.If desired, carry out this reaction in anhydrous conditions to minimize to make the condensation reaction of this silanol polydiorganosiloxane.In certain embodiments, silanol stopped polydiorganosiloxane and end-caps are dissolved in organic solvent in anhydrous conditions, and react under being allowed to condition at room temperature or under high temperature (being up to the boiling point of this solvent).
organosiloxane resins
Components b in method of the present invention) for comprising [the R of at least 60 % by mole in its formula
2siO
3/2] organosiloxane resins of siloxy units, wherein each R
2be C independently when occurring at every turn
1to C
20alkyl, and 1-30 % by mole (such as 1-10 % by mole, 1-5 % by mole, 5-15 % by mole, 15-20 % by mole, 20-25 % by mole, 25-30 % by mole, 5-10 % by mole, 10-15 % by mole, 10-20 % by mole or 20-30 % by mole) siloxy units contain Si-E key, wherein E is the hydrolysable group containing at least one carbon atom.Organosiloxane resins can contain other M, D and Q siloxy units of any amount and array configuration, and prerequisite is that organosiloxane resins contains at least 70 % by mole of [R
2siO
3/2] siloxy units, or organosiloxane resins contains the [R of at least 80 % by mole
2siO
3/2] siloxy units or organosiloxane resins contain the [R of at least 90 % by mole
2siO
3/2] siloxy units or organosiloxane resins contain the [R of at least 95 % by mole
2siO
3/2] siloxy units.In certain embodiments, organosiloxane resins is containing having an appointment [the R of 70 to about 100 % by mole
2siO
3/2] siloxy units, the according to appointment [R of 70 to about 95 % by mole
2siO
3/2] [the R of siloxy units, about 80 to about 95 % by mole
2siO
3/2] [the R of siloxy units or about 90 to about 95 % by mole
2siO
3/2] siloxy units.Can be used as components b) organosiloxane resins comprise those that be called " silsesquioxane " resin.
When occurring at every turn, each R in above organosiloxane resins
2be C independently
1to C
20alkyl (such as C
1to C
10alkyl), wherein alkyl can be alkyl, aryl or alkaryl independently.Each R
2can be C independently when occurring at every turn
1to C
20(such as C
1to C
10alkyl) alkyl, or each R
2can be C independently when occurring at every turn
1to C
8alkyl.Or, when occurring at every turn, each R
2can be C independently
1to C
6alkyl, such as methyl, ethyl, propyl group, butyl, amyl group or hexyl.Or, when occurring at every turn, each R
2can be methyl independently.Each R
2can be aryl, such as phenyl, naphthyl or anthryl independently when occurring at every turn.Or, when occurring at every turn, each R
2can be any combination of aforesaid alkyl or aryl independently.Or, when occurring at every turn, each R
2can be phenyl or methyl independently, make in certain embodiments, each disiloxy unit can have two alkyl (such as two methyl); Two aryl (such as two phenyl); Or alkyl (such as methyl) and aryl (such as phenyl).
Weight-average molecular weight (the M of organosiloxane resins
w) unrestricted, but in certain embodiments 1000 to 10000 or 1500 to 5000g/mol scope in.
Containing [the R of such as at least 80 % by mole
2siO
3/2] organosiloxane resins and preparation method thereof of siloxy units is known in the art.They are hydrolyzed in organic solvent by the organosilane on the silicon atoms with three hydrolysable group (such as halogen or alkoxyl group) and are prepared in certain embodiments.Representative example for the preparation of silsesquioxane resins is found in U.S. Patent No. 5, and 075,103.In addition, the commercially available acquisition of many organosiloxane resins selling as solid (thin slice or powder) or be dissolved in organic solvent.Can be used as components b) suitable non-limiting commercially available organosiloxane resins comprise: Dow
217 flaky resins (Flake Resin), 233Flake, 220Flake, 249Flake, 255Flake, Z-6018Flake (available Dow Corning Corporation).
Those skilled in the art recognizes, [the R containing so high amount
2siO
3/2] organosiloxane resins of siloxy units can have certain density Si-OZ, wherein Z can be hydrogen (i.e. silanol), alkyl (making OZ be alkoxyl group), or OZ also can be any as described herein " E " hydrolysable group.Can easily pass through with the Si-OZ content that the molar percentage of whole siloxyies that organosiloxane resins exists represents
29si NMR measures.The concentration of the OZ group that organosiloxane resins exists can change according to preparation method and to the subsequent disposal of resin.In certain embodiments, silanol (Si-OH) content being applicable to the organosiloxane resins of the inventive method can have the silanol content of at least 5 % by mole or at least 10 % by mole or 25 % by mole or 40 % by mole or 50 % by mole.In other embodiments, silanol content is about 5 % by mole to about 60 % by mole, such as about 10 % by mole to about 60 % by mole, about 25 % by mole to about 60 % by mole, about 40 % by mole to about 60 % by mole, about 25 % by mole to about 40 % by mole or about 25 % by mole to about 50 % by mole.
Those skilled in the art also recognize, [the R containing so high amount
2siO
3/2] organosiloxane resins of siloxy units and silanol content also can retain water molecules, especially under high humidity conditions.Thus, in step I) in reaction before to remove by " drying " organosiloxane resins the excessive water that resin exists be usually favourable.This is by being dissolved in organic solvent by this organosiloxane resins, being heated to backflow and removing water to realize by isolation technique (such as Dean-Stark separator or equivalent method).
Select step I) reaction in amount a) and b) used to provide [the R of the disiloxy unit with 5 to 65 % by mole
1 2siO
2/2] and the trimethylsilane oxygen base unit [R of 35 to 95 % by mole
2siO
3/2] resin-linear Organosiloxane block copolymer.Component a) and b) in % by mole can easily the using of the disiloxy unit that exists and trimethylsilane oxygen base unit
29si NMR technical measurement.Starting molar % then deciding step I) in component quality a) and b) used.
In certain embodiments, component amount a) and b) can be selected to guarantee that the amount relative to added linear organosiloxane exists the silanol of molar excess on organosiloxane resins.Thus, should add enough organosiloxane resins with in certain embodiments with step I) in whole linear organosiloxane used react.Therefore, the organosiloxane resins of molar excess can be used.Amount used is by considering that the mole number of the organosiloxane resins that every mole of linear organosiloxane is used is determined.In order to explain the typical calculation of component amount a) and b), the number-average molecular weight of 28 % by weight can be used for about 1,200g/mol (M
n) Dow
217flake resin and 72 % by weight M
nfor the silanol stopped PDMS (Gelest DMS-S27) of about 13,500g/mol.When by Dow
when 217flake is used for according to method synthetic copolymer as herein described, the ratio [(28/1200)/(72/13500)] of 4.38 of molecular resin and PDMS molecule can be obtained, and thus excessive molecular resin and substantially all PDMS molecular reactions are provided, the PDMS molecule of major part (such as at least 95 % by weight) is incorporated in multipolymer.
As discussed herein, step I) in the reaction that realizes be condensation reaction between silanol on the hydrolysable group of linear organosiloxane and organosiloxane resins.In certain embodiments, the silanol of q.s stay formed resin-linear organosiloxane copolymer resin Composition on the Step II in the inventive method) in react further.In certain embodiments, the step I of the inventive method stayed by the silanol of at least 10 % by mole or at least 20 % by mole or at least 30 % by mole) in prepared resin-linear organosiloxane copolymer trimethylsilane oxygen base unit on.In certain embodiments, about 10 % by mole to about 60 % by mole (such as about 20 % by mole to about 60 % by mole or about 30 % by mole to about 60 % by mole) stay the step I of the inventive method) in prepared resin-linear organosiloxane copolymer trimethylsilane oxygen base unit on.
The reaction conditions that above-mentioned (a) linear organosiloxane and (b) organosiloxane resins are reacted is unrestricted.In certain embodiments, selective reaction condition realizes a) linear organosiloxane and condensed type b) between organosiloxane resins and reacts.Multiple non-limiting example and reaction conditions is described in " example " herein.In certain embodiments, (a) linear organosiloxane and (b) organosiloxane resins at room temperature react.In other embodiments, (a) and (b) react at the temperature exceeding room temperature, and this temperature range is up to about 50 DEG C, 75 DEG C, 100 DEG C, or are even up to 150 DEG C.Or (a) and (b) one can to react when solvent refluxing.In other embodiments, (a) and (b) react at lower than room temperature 5 DEG C, 10 DEG C or temperature even more than 10 DEG C.In other embodiments, (a) is 1,5,10,30,60,120 or 180 minute with the reaction times of (b), or even longer.In certain embodiments, (a) and (b) react under inert atmosphere (such as nitrogen or rare gas).Or (a) and (b) can react under the atmosphere comprising some water vapors and/or oxygen.In addition, (a) and (b) can adopt any equipment (comprising mixing tank, vortex vibrator, agitator, well heater etc.) to react in the container of any size.In other embodiments, (a) reacts in one or more organic solvents (can be polarity or nonpolar) with (b).In certain embodiments, aromatic solvent, such as toluene, dimethylbenzene, benzene etc. are used.The amount being dissolved in the organosiloxane resins in organic solvent can change to some extent, but can for the amount making the too early condensation of the chain extension of this linear organosiloxane or this organosiloxane resins minimum.
AddO-on therapy order a) and b) can change.In certain embodiments, linear organosiloxane is added the solution of dissolving organosiloxane resins in organic solvent.This order of addition can strengthen the condensation of the hydrolysable group on linear organosiloxane and the silanol on organosiloxane resins, makes the too early condensation of the chain extension of this linear organosiloxane or this organosiloxane resins minimum simultaneously.In other embodiments, organosiloxane resins is added the solution of dissolving linear organosiloxane in organic solvent.
Step I) in extent of reaction and resin-linear Organosiloxane block copolymer formation by multiple analytical technology (such as GPC, IR or
29si NMR) monitor.In certain embodiments, allow step I) in reaction continue until the step I of at least 95 % by weight (such as at least 96%, at least 97%, at least 98%, at least 99% or 100%)) in linear organosiloxane used be incorporated in resin-linear Organosiloxane block copolymer.
The Step II of the inventive method) relate to and will derive from step I) resin-linear Organosiloxane block copolymer contact the silanol content of resin-linear Organosiloxane block copolymer to be reduced to 5 % by mole or less (such as, be less than 5 % by mole with alkali thickening agent; Be less than the silanol of 4 % by mole; Be less than the silanol of 3 % by mole; Be less than the silanol of 2 % by mole; Be less than the silanol of 1 % by mole; About 1 to the silanol being less than 5 % by mole; About 2 to the silanol being less than 5 % by mole; About 3 to the silanol being less than 5 % by mole; About 0.5 to the silanol being less than 5 % by mole; The silanol of about 0.5 to about 4 % by mole; The silanol of about 0.5 to about 2 % by mole; The silanol of about 1.5 to about 3.7 % by mole; The silanol of about 2 to about 4 % by mole; Or the silanol of about 0.5 to about 1 % by mole).
Step II) derive from step I by " alkali thickening ") resin-linear Organosiloxane block copolymer and complete.As used herein, " alkali thickening " makes a general reference the base catalyzed condensation of the silanol on silicone resin, generates the water as by product.In certain embodiments, this type of thickening reaction increases resin solvability in organic solvent and/or avoids silicone resin generation gelling.According to method of the present invention, Step II is carried out alkali thickening as the highly basic of catalyzer by adding and is realized.Alkaline catalysts includes but not limited to alkali metal hydroxide, comprises NaOH and KOH, or the combination of one or more alkali metal hydroxides.In certain embodiments, alkaline catalysts is KOH.The completing by stopping producing the water that formed as byproduct of reaction and confirmed of condensation reaction.
The amount of the alkali that resin of thickening-linear organosiloxane segmented copolymer and other resin Compositions add can change and unrestricted to some extent.In certain embodiments, add enough amounts to realize following two aspects: in and in step I) in produce acidic by-products (if yes) (such as acetic acid), and alkali thickening derives from step I) resin-linear Organosiloxane block copolymer.In certain embodiments, the KOH aqueous solution (solution of such as 10 % by weight, the solution of 20 % by weight, 30 % by weight solution, 40 % by weight solution, 50 % by weight solution, 70 % by weight solution, 80 % by weight solution, containing have an appointment 10 % by weight to about 80 % by weight solution or containing have an appointment 30 % by weight to about 50 % by weight solution) can be used as catalyzer and with enough amounts add so that the linear organosiloxane copolymer solid of per unit resin provides the KOH of 0.05 to 0.15 % by weight in reaction mixture.In certain embodiments, KOH methanol solution can be used.
Step II I in the inventive method) be optional, and relate to processing resin-linear Organosiloxane block copolymer further.As used herein, phrase " further processing " refers to any further reaction of formed resin-linear organosiloxane copolymer or processes to strengthen its package stability and/or optical clarity etc.In Step II) in the resin-linear organosiloxane copolymer that produces still can containing " OZ " group (namely, ≡ SiOZ group, wherein Z represents H, makes group ≡ SiOZ represent silanol or other hydrolysable group, the alkoxyl group such as represented by-OZ).Being present in OZ group on resin-linear organosiloxane copolymer in this stage can for being present in Step II at first) in resin Composition on silanol.It is possible that at lay up period, this type of " OZ " group can react further, thus limit frame hides stability, or weakens the reactivity of resin-linear organosiloxane copolymer during final application.Or the further reaction of remaining silanol can strengthen the formation in resin territory further and improve the optical clarity of this resin-linear organosiloxane copolymer.Thus, can optional Step II I be carried out) to make Step II further) in preparation Organosiloxane block copolymer on exist OZ reaction to improve package stability and/or optical clarity.For Step II I) condition can change to some extent according to the selection of linear component and resin Composition, their amount and end-caps used.
In an embodiment of the method, Step II I) by making from Step II) resin-linear organo-siloxane and water react and remove any micromolecular compound (such as acetic acid) formed in the method and carry out.In certain embodiments, the resinous organosiloxane that resin-linear organosiloxane copolymer is acetoxyl group by wherein E produces, and/or in Step II) in use acetoxysilane.Although do not wish to be bound by any theory, it is possible that in certain embodiments, Step II) in the resin-linear organo-siloxane that formed contain hydrolyzable Si-O-C (O) CH of significant quantity
3group, it can limit the package stability of this resin-linear organosiloxane copolymer.Thus, can add water in the resin-linear organosiloxane copolymer formed by Step II, Si-O-C (O) CH that its hydrolyzable is a large amount of
3group to be cross-linked trimethylsilane oxygen base unit further, and eliminates acetic acid.The acetic acid formed and any excessive water remove by known isolation technique.The amount of the water added can change in certain embodiments to some extent.In certain embodiments, the amount of the water added can be 10 % by weight, or every total solid (the resin-linear organosiloxane copolymer in reaction medium) adds 5 % by weight.
In an embodiment of the method, Step II I) by making from Step II) resin-linear organo-siloxane and end-caps (comprising the end-caps being selected from alcohol, oxime or trialkylsiloxy compound) react to carry out.In certain embodiments, the linear organosiloxane that resin-linear organosiloxane copolymer can be oximido by wherein E produces.End-caps can be C
1-C
20alcohol (such as C
1-C
20alcohol, C
1-C
12alcohol, C
1-C
10alcohol, C
1-C
6alcohol or C
1-C
4alcohol), other alcohol in such as methyl alcohol, ethanol, propyl alcohol, butanols or this series.Or this alcohol is propyl carbinol.This end-caps can also be trialkylsiloxy compound, as trimethylmethoxysilane or trimethylethoxysilane.The amount of end-caps can change to some extent.In certain embodiments, relative to the linear Organosiloxane block copolymer solid of the resin in reaction medium, the amount of end-caps can between 3 and 15 % by weight (such as 3 to 10 % by weight, 5 to 15 % by weight, 3 to 5 % by weight, 10 to 15 % by weight, 5 to 10 % by weight or 3 to 12 % by weight).
Optional step III in method) can or replace except " further process " " processing further ", relate to and will derive from Step II) resin-linear Organosiloxane block copolymer contact with stablizer or super base.
At Step II I) another embodiment in, add acid (such as acetic acid) with neutralization procedure II with enough amounts) in alkali used.
The step IV of the inventive method) be optional, and relate to remove step I) and reaction II) in organic solvent used.This organic solvent removes by any known technology.In certain embodiments, organic solvent is removed by atmospheric conditions or under reduced pressure heat resin-linear organosiloxane copolymer composition.In certain embodiments, all solvents are not removed.In certain embodiments, remove the solvent of at least 20%, at least 30%, at least 40% or at least 50%, such as, remove the solvent of at least 60%, at least 70%, at least 75%, at least 80% or at least 90%.In certain embodiments, remove the solvent being less than 20%, such as, remove the solvent being less than 15%, being less than 10%, being less than 5% or 0%.In other embodiments, remove the solvent of about 20% to about 100%, such as, remove about 30% to about 90%, about 20% to about 80%, about 30 to about 60%, about 50 to about 60%, about 70 to about 80% or the solvent of about 50% to about 90%.
Some in the embodiment of the present invention relate to the optical module and goods that comprise composition as herein described, those described in the PCT/US2013/025126 that the PCT/US2013/021707 and 2013 submitted in the PCT/US2012/071011 such as submitted on December 20th, 2012, on January 16th, 2013 submits to 7, on February, these patents are all incorporated to way of reference, as herein complete illustrate.Therefore, some embodiments of the present invention relate to the LED agent comprising Organosiloxane block copolymer as herein described.
As used herein, term " about " permissible value or scope can have fluctuation to a certain degree, such as in 10% of the limit value of described value or described scope, in 5% or in 1%.
The numerical value as range limit not only comprising and clearly listing should be interpreted as in a flexible way using the value that range format is expressed, but also comprise and be encompassed in all single numerical value within the scope of this or sub-range, be expressly recited out just as each numerical value and sub-range.Such as, the scope of " about 0.1% to about 5% " or " about 0.1% to 5% " should be understood to not only comprise about 0.1% to about 5%, also be included in single value in institute's how (as, 1%, 2%, 3% and 4%) and sub-range (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%).
As herein described and claimed embodiments of the invention will not be limited to specific embodiment disclosed herein in scope, because these embodiments are intended to illustrate many aspects of the present disclosure.Any equivalent integers is intended to drop in the scope of the present disclosure.In fact, except those embodiments illustrated herein and describe, will be apparent to those skilled in the art by aforementioned explanation to the various amendments of embodiment.This type of amendment is also intended to fall within the scope of the appended claims.
Provide specification digest and determine character disclosed in technology rapidly to allow reader.Should be appreciated that it can not be used for explaining or limiting scope or the implication of claims.
example
Following instance is included to set forth specific embodiments of the invention.But, it should be appreciated by those skilled in the art according to the disclosure, can in disclosed specific embodiment, make many changes and still can obtain similar or identical result and not deviate from the spirit and scope of the present invention.All per-cent is all in % by weight.Except as otherwise noted, otherwise all measurements all carry out at 23 DEG C.
characterization technique
29
si and
13
c NMR composes
By will about 3 grams of solventfree resin-linear copolymers (by by sample at room temperature dried overnight and prepare), 1 gram of CDCl
3with the Cr (acac) of 4 grams of 0.04M
3cDCl
3solution to take in bottle and thoroughly mixing and prepared the NMR sample of resin linear product.Then sample is shifted into without in silicon NMR pipe.Collection of illustrative plates is obtained with Varian Mercury 400MHz NMR.By 4 grams of diluted samples being entered the Cr (acac) of 4 grams of 0.04M
3cDCl
3solution and prepared the NMR sample of the other materials of such as 217Flake and silanol stopped PDMS.
13c NMR experiment is carried out as follows.Sample is placed in 16mm glass NMR pipe.5mm NMR pipe is put into 16mm manage and fill lock field solvent.Obtained in 12 or 20 minutes signal averaging periods
13c DEPT NMR.?
1h operating frequency be 400MHz Varian Inova NMR spectrometer on obtain data.
The silanol content of resin-linear product by
29t (Ph, OZ) during Si NMR composes and the integrated value in T (Ph, OZ2) district calculate.T (alkyl) group be regarded as complete condensation (assuming that) and to deduct from T (Ph, OZ) district.T (alkyl) content will be by deriving from
29the integrated value of the D (Me2) of Si NMR is multiplied by a point rate (the Si mole number of the Si mole number/PDMS of coupling agent used in synthesizing formula) and calculates.Isopropoxy from 217Flake is not deducted, because its concentration is low from OZ value.Therefore, assuming that the total OH of total OZ=.
gpc analysis
In regular grade THF, prepare sample with 0.5%w/v concentration, filter with 0.45 μm of PTFE syringe filter, and analyze relative to polystyrene standards.Be 580 to 2,320,000 daltonian 16 kinds of polystyrene standards for the relative calibration (three rank matchings) of molecular weight determination based on molecular weight ranges.By being furnished with Waters 2695 separation module of vacuum degasser, Waters 2410 differential refractometer and being connected to two (300mm × 7.5mm) Polymer Laboratories Mixed C posts of guard column above, (molecular weight separating ranges is 200 to 3 to chromatographic separation equipment; 000,000) form.Use the regular grade THF being programmed into 1.0mL/min flow velocity to be separated, sampling volume is set to 100 μ L and post and detector are heated to 35 DEG C.Collect the data of 25 minutes and use Atlas/Cirrus software to process.
In order to measure free resin content, by the free resin peak integration at lower molecular weight place to obtain area percentage.
rheology analysis
Delaware State Newcastle TA instrument company (TA Instruments will be derived from, New Castle, DE19720) the commercially available rheometer with forced convection oven (there is the ARES-RDA of 2KSTD standard ball pivot spring transverter) for measuring temperature variant storage modulus (G '), out-of-phase modulus (G ") and loss tangent.Test specimen (such as wide 8mm, thick 1mm) is carried between parallel plate and also measures with small strain oscillatory rheometer, with 2 DEG C/min, temperature is risen to 300 DEG C (frequency is for 1Hz) from 25 DEG C simultaneously.
In order to characterize multipolymer, by flowing initial calculation be G ' decline time inflection temperature (being designated as FLOW), the tolerance that viscosity when 120 DEG C will be reported as melt-processible, solidification initial calculation is the inflection temperature (be designated as CURE) of G ' when rising.
optical clarity
Optical clarity is evaluated as the transmittance percentage that wavelength is the light of about 350-1000 nanometer, and its thick sample of 1mm being through the cast sheet material of the present composition is measured.The sample of the percent transmission with at least 95% is considered as optically transparent.
the preparation of the Ph-T – 230dp PhMe of example 1:60 % by weight
example 1
500mL 4 neck round-bottomed flask is loaded onto toluene (60.00g) and 217flake resin (60.0g, 0.439mol Si).Flask is furnished with thermometer, teflon stirring rake and is attached to the Dean Stark device of water cooled condenser.Apply blanket of nitrogen.To Dean Stark device preliminary filling toluene.Oil bath is used for heating.
Reaction mixture is heated 30 minutes under reflux, at this moment, removes 0.30mL water.Reaction mixture is cooled to 108 DEG C (still temperature).
By toluene (18.46g) solution (61.54g solution=40.0g siloxanes of silanol stopped PhMe siloxanes, 0.293 mole of Si) with 50/50 methyl triacetoxysilane/ethyltriacetoxysilane (MTA/ETA) (0.60g, 0.00260 mole of Si) end-blocking.The PhMe siloxanes of end-blocking preparation (same day) in glove box under a nitrogen in the following way: add 50/50MTA/ETA and at room temperature mix 1 hour in siloxanes.
PhMe siloxane polymer solution is added 217flake solution fast at 108 DEG C.Reaction mixture is heated 2 hours under reflux, during this period, removes 0.32mL water.
Use KOH (counting 0.1 % by weight by solid) to carry out alkali thickening in the following manner: reaction mixture to be cooled to 95 DEG C, then add water-soluble 10% KOH solution (altogether 5.36g:4.36g in order in and acetic acid and 1.00g is linear in order to resin of thickening): 4.36g solution=0.436g solid=0.00777 mole; 1.00g solution=0.100g solid=0.00178 mole.
Reaction mixture is heated 1 hour under reflux, at this moment, removes 7.28mL water.Reaction mixture is allowed to be cooled to room temperature.
With in the toluene solution (1.60g solution=0.160g acid=0.00266 equimolar acid) of the Glacial acetic acid of 10% and KOH.Stoichiometry 1.5 equimolar acid: 1.0 moles of KOH.
Reaction mixture is at room temperature mixed and spends the night, and at second day by 1.2 μm of filter press filtration.Analytical test confirms resin-linear organosiloxane copolymer and has average formula D
phMe 0.398t
ph 0.591with the silanol content of 2.11 % by mole.Sample containing non-volatile matter (NVC) is transparent.
example 2-5
According to the program of example 1, but the amount of resin and linear component changes to some extent, has prepared other resin-linear Organosiloxane block copolymer, as in following table 1 gather.
comparative example 1
To altogether 503.4 grams of (2.54 moles) phenyltrimethoxysila,e and 0.36 gram of trifluoromethanesulfonic acid (gram acid of trifluoro profit) join in the 1L 3 neck round-bottomed flask being furnished with mechanical stirring axle, thermometer, Dean-Stark separator, condenser and nitrogen inlet and outlet.When at 200 rpm mixture being stirred, altogether slowly will add in 15 minutes by 137.2g (7.62 moles) water, guarantee that reaction mixture temperature is no more than 50 DEG C.Then, at 75 DEG C to reaction mixture refluxed 90 minutes.By Dean-Stark separator removing methyl alcohol and some water.After temperature rises to 80 DEG C, remove about 233 grams of liquid.Subsequently, reaction mixture is cooled to about 60 DEG C, and adds the KOH aqueous solution of 317 grams of toluene and 1.54 gram 50 % by weight separately.Reaction mixture is refluxed, removes water by Dean-Stark separator.After temperature rises to 113 DEG C, remove about 300 grams of liquid.After mixture is refluxed 2 hours, reaction mixture is cooled to 90 DEG C again, and in mixture, adds 0.83 gram of acetic acid.Then reaction mixture is cooled 30 minutes again, by Bo Lixianwei/Bu Shi funnel, the salt formed is filtered, to be separated and to collect salt.Then use Rotary Evaporators except desolventizing, and collect peel ply resin.The molecular weight of this resin is about 19,800kg/mol.
Table 1 – 4 summarizes character and the performance of the resin-linear Organosiloxane block copolymer prepared according to method as herein described.
table 1
| Example | % by weight Ph-T | PhMe?dp | Mw，g/mol | OZ, % by mole | Muddy/transparent |
| Comparative example 1 | 100 | Nothing | 19,800 | 2.1 | Transparent |
| Comparative example 2 | 100 | Nothing | 12,400 | 1.8 | Transparent |
| 2 | 90 | 230 | 16,600 | 0.7 | Slightly muddy |
| 3 | 80 | 230 | 3.7 | Muddy | |
| 4 | 70 | 230 | 2.5 | Muddy | |
| 5 | 60 | 230 | 2.1 | Transparent | |
| 1 | 45 | 117 | 25,100 | 1.8 | Transparent |
table 2
Sample in table 2 is by preparing 1g sample deposition in the independent vessel of weighing.These samples were warming up to 250 from 40 and solidify in an oven in one hour.The thermogravimetric analysis (TGA) (rising to 600 DEG C with 10 DEG C/min in atmosphere) of these samples gives the (T of the decomposition temperature shown in table 2
d), 5% result, wherein (T
d), 5% corresponds to temperature when sample weight loss 5 % by weight.Also the sample prepared in a similar manner is placed in toluene and butylacetate bottle two days to test solvability.Also have recorded the visual appearance about brittleness and crusher surface.
Following table 3 shows the glass transition (T of selected sample
g) and flow initial.
table 3
Following table 4 shows the snappiness data (mandrel test (ASTM D1737)) of selected sample.
table 4
| Example | 1 mil blade coating on Al substrate | 2 mil blade coatings on Al substrate | 4 mil blade coatings on Al substrate |
| Comparative example 1 | Transparent film, > 1 inch | Broken film, > 1 inch | Serious fragmentation, > 1 inch |
| 5 | Transparent film, < 1/8 inch | Transparent film, < 1/8 inch | Transparent film, > 1 inch |
| 1 | Transparent film, < 1/8 inch | Transparent film, < 1/8 inch | Transparent film, < 1/8 inch |
In brief, mandrel testing apparatus is the cylindrical steel bar of the six roots of sensation of 1 inch, 3/4 inch, 1/2 inch, 7/16 inch, 3/8 inch, 5/16 inch, 1/4 inch, 3/16 inch and 1/8 inch by diameter and forms at their device of test period support.Be placed in above mandrel by the plate of band coating, the side of band coating does not contact with mandrel, and there is the overhang of at least 2 inches every side.Be taken at the minimum diameter that breaks at curved edge place as flexibility results.
With the drawdown rod of 1,2 and 4 mils by film from the solution blade coating of about 50% solid on aluminium sheet.Sample is solidified 3 hours at 160 DEG C, then observes transparency, initial film outward appearance carry out mandrel test.
Claims (24)
1., for the preparation of a method for organopolysiloxane segmented copolymer, comprising:
I) make
A) there is the linear organosiloxane of following formula:
R
1 q(E)
(3-q)SiO(R
1 2SiO
2/2)
nSi(E)
(3-q)R
1 q，
Wherein each R
1be C independently when occurring at every turn
1to C
30alkyl or the hydrolysable group containing at least one carbon atom,
N is 10 to 400,
Q is 0,1 or 2,
E is the hydrolysable group containing at least one carbon atom, and
B) in its formula, comprise [the R of at least 60 % by mole
2siO
3/2] organosiloxane resins of siloxy units, wherein each R
2be C independently when occurring at every turn
1to C
20alkyl,
React in c) organic solvent
To form resin-linear Organosiloxane block copolymer;
Wherein select step I) in amount a) and b) used to provide [the R of the disiloxy unit with 5 to 65 % by mole
1 2siO
2/2] and the trimethylsilane oxygen base unit [R of 35 to 95 % by mole
2siO
3/2] described resin-linear Organosiloxane block copolymer, and
The wherein step I of at least 95 % by weight) in described linear organosiloxane used be incorporated in described resin-linear Organosiloxane block copolymer;
II) will step I be derived from) described resin-linear Organosiloxane block copolymer contact the silanol content of described resin-linear Organosiloxane block copolymer to be reduced to 5 % by mole or less with alkali thickening agent;
III) optionally, described resin-linear Organosiloxane block copolymer is processed further; And
IV) optionally, described organic solvent is removed.
2. method according to claim 1, wherein said alkali thickening agent comprises highly basic.
3. method according to claim 2, wherein said highly basic comprises KOH or NaOH.
4. according to method in any one of the preceding claims wherein, wherein R
2for phenyl.
5. method according to claim 1 and 2, wherein R
1for phenyl or methyl.
6. method according to claim 1 and 2, wherein said disiloxy unit has formula [(CH
3) (C
6h
5) SiO
2/2].
7. method according to claim 1, wherein said further processing comprises and will derive from Step II) described resin-linear organo-siloxane contact with water and remove acetic acid.
8. method according to claim 1, wherein said further processing comprises and will derive from Step II) described resin-linear organo-siloxane contact with the end-caps being selected from alcohol, oxime or trialkylsiloxy compound.
9. method according to claim 1, wherein replaces described further processing or except described further processing, will derive from Step II) described Organosiloxane block copolymer contact with stablizer or super base.
10. by organopolysiloxane segmented copolymer prepared by the method according to any one of the claims.
11. organopolysiloxane segmented copolymers according to claim 10, wherein said organopolysiloxane segmented copolymer is Step II) reaction product.
12. 1 kinds of compositions, comprise organopolysiloxane segmented copolymer according to claim 10.
13. compositions according to claim 12, described composition is curable.
14. compositions according to claim 12, described composition is solid.
The cured product of 15. compositions according to claim 13 or 14.
16. 1 kinds of solid film compositions, comprise the composition according to claim 12-15.
17. solid film compositions according to claim 16, wherein said solids composition has the transmittance of at least 95%.
18. 1 kinds of LED agent, comprise the composition according to claim 12-17.
19. 1 kinds of linear Organosiloxane block copolymer of resin, comprise:
Formula [the R of 5 % by mole to 65 % by mole
1 2siO
2/2] disiloxy unit,
Formula [the R of 35 % by mole to 95 % by mole
2siO
3/2] trimethylsilane oxygen base unit,
5 % by mole or less silanol [≡ SiOH],
The wherein R when occurring at every turn
1be C independently
1to C
30alkyl,
The R when occurring at every turn
2be C independently
1to C
20alkyl, and
Wherein:
Described disiloxy unit [R
1 2siO
2/2] with
Each linearity block has average 10 to 400 disiloxy unit [R1
2siO
2/2]
Linearity block arranges,
Described trimethylsilane oxygen base unit [R
2siO
3/2] with
Molecular weight is the non-linear block arrangement of at least 500g/mol,
Each linearity block is connected at least one non-linear block, and
The molecular weight of described Organosiloxane block copolymer is at least 5,000g/mol.
20. Organosiloxane block copolymer according to claim 19, wherein each R
2for phenyl.
21. Organosiloxane block copolymer according to claim 19 or 20, wherein each R
1be methyl or phenyl independently when occurring at every turn.
22. Organosiloxane block copolymer according to claim 19 or 20, wherein said disiloxy unit has formula [(CH
3) (C
6h
5) SiO
2/2].
23. Organosiloxane block copolymer according to claim 19 or 20, wherein said disiloxy unit has formula [(CH
3)
2siO
2/2].
24. 1 kinds of curable compositions, comprise the Organosiloxane block copolymer according to claim 20-23 and organic solvent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261613532P | 2012-03-21 | 2012-03-21 | |
| US61/613,532 | 2012-03-21 | ||
| PCT/US2013/030378 WO2013142138A1 (en) | 2012-03-21 | 2013-03-12 | Compositions of resin-linear organosiloxane block copolymers |
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|---|---|
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| CN104271641B CN104271641B (en) | 2016-11-02 |
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| Country | Link |
|---|---|
| US (1) | US9181402B2 (en) |
| EP (1) | EP2828316B1 (en) |
| JP (1) | JP6170129B2 (en) |
| KR (1) | KR102086317B1 (en) |
| CN (1) | CN104271641B (en) |
| WO (1) | WO2013142138A1 (en) |
Cited By (3)
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|---|---|---|---|---|
| US9181402B2 (en) | 2012-03-21 | 2015-11-10 | Dow Corning Corporation | Compositions of resin-linear organosiloxane block copolymers |
| CN108699389A (en) * | 2016-02-24 | 2018-10-23 | 日产化学株式会社 | Pattern reversion coating agent containing silicon |
| CN109790414A (en) * | 2016-10-04 | 2019-05-21 | 日产化学株式会社 | Coating composition for pattern reversion |
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|---|---|---|---|---|
| WO2014152522A1 (en) * | 2013-03-15 | 2014-09-25 | Dow Corning Corporation | Compositions of resin-linear organosiloxane block copolymers |
| EP3098266A4 (en) * | 2014-01-24 | 2017-10-04 | Sumitomo Chemical Company Limited | Liquid silicone resin composition |
| US9534089B2 (en) * | 2014-07-11 | 2017-01-03 | The Boeing Company | Temperature-resistant silicone resins |
| TWI678551B (en) | 2015-07-28 | 2019-12-01 | 美商道康寧公司 | Smart optical materials, formulations, methods, uses, articles, and devices |
| US10874604B2 (en) | 2016-10-04 | 2020-12-29 | Dow Toray Co., Ltd. | Cosmetic composition or external composition, and cosmetic raw material composition |
| US11015082B2 (en) * | 2017-12-19 | 2021-05-25 | Honeywell International Inc. | Crack-resistant polysiloxane dielectric planarizing compositions, methods and films |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2828316B1 (en) | 2017-02-22 |
| JP6170129B2 (en) | 2017-07-26 |
| US9181402B2 (en) | 2015-11-10 |
| KR20140137440A (en) | 2014-12-02 |
| US20150087772A1 (en) | 2015-03-26 |
| CN104271641B (en) | 2016-11-02 |
| WO2013142138A1 (en) | 2013-09-26 |
| KR102086317B1 (en) | 2020-03-09 |
| JP2015518062A (en) | 2015-06-25 |
| EP2828316A1 (en) | 2015-01-28 |
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